UV FLEXO INK COMPOSITION AND SURFACE TREATMENT EFFECTS ON

ADHESION TO FLEXIBLE PACKAGING

Enercon Industries Corporation
Charles Henderson, Cytec Industries Inc.
Andrew Seecharan, Cytec Industries Inc.
ABSTRACT
UV flexo inks are becoming increasingly popular in flexible packaging and shrink sleeve
applications, traditional markets for flexographic inks. The ever-increasing improvements in UV
flexo inks such as print quality, low ink maintenance requirements, no solvents, high press
stability, and in-line finishing have all contributed to converters decisions to switch to UV flexo
system. Recently, new UV flexo ink systems have improved efficiency and production speeds to
greater than 250 meters/minute. However, variables such as resin selection, amount of ink
applied, substrate absorbency, UV curing conditions and print speed can all propagate episodes
of erratic adhesion on difficult substrates. Hence, many substrates are coated with a primer to
perform as adhesion promoter. Nevertheless, this additional coating are not always successful,
increase cost to the convertor and typically do not mitigate the migrating effect of lubricating
additives found within certain flexible packaging films. This paper will detail, in the absence of
adhesion promoters, the effects of corona, flame or atmospheric plasma surface treatments on the
adhesion of UV flexo inks to flexible packaging films.
INTRODUCTION
UV flexo technology is quickly establishing itself as a bridge to sustainability within the
graphic arts markets. Historically, energy-curable systems were used in surface printing
applications (PSA labels, shrink sleeves, in-mold, food packaging, etc.) where the properties of
cured UV inks and coatings led to improvements in abrasion resistance compared to solvent- and
water-based inks. It was also found that UV inks performed well with UV and EB coatings used
in flexible packaging structures. Currently, UV flexo inks are being applied on the internal and
external surfaces of a broad range of high performance packaging structures. In addition, UV
flexo inks provide a significant step toward sustainability by eliminating/reducing the emissions
of VOCs and CO2.
Generally speaking, the drying of a conventional ink film occurs when the ink solids
(resins, additives, pigment, etc.) coalesce into a film on the substrate surface accompanied by
evaporation of volatiles and/or penetration into the base substrate. In some cases, conventional
inks require several hours for complete drying. With energy-cured materials, the majority of the
components in the ink or coating remains on the surface of the substrate and are chemically
converted within seconds to a hard surface film following exposure to UV or EB energy. The
difference between these processes lies in the chemistry of the materials in the inks and coatings,
and in the technology required to energize the curing process.
The formulation of UV flexo inks with low viscosity, high color strength, high cure
speeds and adhesion is a considerable challenge for ink formulators. The rheology of UV flexo
inks is significantly improved with measured combinations of resins, additives and pigment
wetting vehicles. Oligomers are the primary resins in an energy-cured ink and provide basic ink
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properties, while monomers are used primarily for viscosity reduction. [1] Relative to optimizing
anchorage of these oligomer-monomer carriers to the substrate, surface modification by corona,
flame or atmospheric plasma all have potential to do so because of their efficient surface
roughening and functionalizing effects.
This collaborative study was undertaken to understand the potential synergistic
interactions between different atmospheric pressure surface modification techniques and
different oligomer types in UV flexo ink formulations, and the overall impact of these synergies
on ink adhesion to various unprimed, flexible polymer-based surfaces.
EXPERIMENTAL
Ink Materials:

All monomers and oligomers used for this study were supplied by Cytec Industries
(Smyrna, GA).
Table 1. Oligomers evaluated
Products

Description

Functionality

Viscosity
(cP @ 25C)
515

EBECRYL 83

Amine Modified Polyester Acrylate

3.5

EBECRYL 3702

Fatty Acid Modified Epoxy Acrylate

495,000

EBECRYL 4883

Aliphatic Urethane Acrylate

161,000

EBECRYL 860

Epoxidized Oil Acrylate

26,500

EBECRYL 5801

Polyester Acrylate Bioligomer

6,000

EBECRYL 450

Fatty Acid Modified Polyester Acrylate

8,200

EBECRYL 3703

Amine Modified Epoxy Acrylate

320,000

EBECRYL 4827

Aromatic Urethane Acrylate

238,000

EBECRYL 3720

Bisphenol-A Epoxy Acrylate

750,000

The photoinitiator used for this study and also supplied by Cytec Industries (Smyrna,
GA), Additol DX, is a proprietary, eutectic blend of photointiators designed to provide both
surface and through cure.
Surface Treatments:
Surface modification (summarized in Table 2) of the films was completed by Enercon
Industries Corp., Menomonee Falls, WI. The following types of treatment were performed:
1) Universal corona discharge - Technology is a dual dielectric corona system, employing a
ceramic electrode assembly and ceramic-covered ground roll, high voltage/low frequency
transformer and power supply.
2) Flame plasma discharge - Technology employs a high velocity, CNC fabricated port burner
with removable port inserts, water cooled lateral ports integral to the burner assembly,
chilled treater roll, electronic combustion/gas mixing controls, and integrated electronic
oxygen analyzer.
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3) Atmospheric plasma discharge Technology employs proprietary plasma electrode and

ground plane, power supply and transformer. Gas chemistries are regulated and
electronically mixed prior to introduction to the treatment station.
Table 2. Surface Modification Trial Protocol

Plasma
Carrier
Reactive
%
%

Power Density
(W/ft2/min.)

Initial
mN/m

Final
mN/m

CU

35

42

CU

35

42

Material

Corona

PLA
PLA

Flame

PLA

FM

1100 lpm/1200fpm

35

42

PLA

FM

1100 lpm/1200fpm

35

42

PLA

Nitrogen/95

CO2 / 5

35

42

PLA

Nitrogen/95

CO2 / 5

35

42

PET

CU

36

44

PET

CU

36

44

PET

FM

1100 lpm/1200fpm

36

44

PET

FM

1100 lpm/1200fpm

36

44

PET

Nitrogen/95

CO2 / 5

36

44

PET

Nitrogen/95

CO2 / 5

36

44

Met. OPP

CU

2.6

30

44

Met. OPP

CU

2.6

30

44

Met. OPP

FM

1300 lpm / 500fpm

30

44

Met. OPP

FM

1300 lpm / 500fpm

30

44

Met. OPP

Nitrogen/95

CO2 / 5

2.6

30

44

Met. OPP

Nitrogen/95

CO2 / 5

2.6

30

44

Universal corona discharge technology was chosen because of its homogeneous

discharge relative to covered roll and bare roll discharges, offering a higher potential for surface
adhesion. The flame plasma technology employed utilized CNC-drilled high velocity port burner
assemblies and a double-coated chill roll with electronic mass flow control of air and natural gas
inputs at a 10:1 ratio, respectively, and electronic oxygen content control. Atmospheric plasma
treatment ionized a mixture of nitrogen and carbon dioxide using electronic mass flow controls at
high frequency. The uncoated films used in the study are described in Table 3 below.
Table 3. Films evaluated
Material
Biaxially oriented PLA 4042D, 20 microns

Supplier
NatureWorks

AET MT metalized, BOPP film, 18 microns

AET films

Uncoated PET

Teijin DuPont Films Japan Ltd.

Testing:
Bench-evaluations were completed at Cytec Industries using hand-held flexographic print
instruments equipped with a 360 line screen anilox roll and a metal doctor blade. All benchproduced prints were cured in a Fusion Aetek UV unit set at 150 fpm and using 400W/inch
mercury lamps in an air environment. Exposure was 120 mJ/cm2.
Starting formulations identified by bench-evaluation were subsequently tested on a twounit Aquaflex LC-1002 printing press using the same films as in bench-testing. Press evaluation
was completed at line speeds between 150 and 350 feet per minute (fpm). On press, the inks
were printed with a 700 line screen/2.43 BCM anilox roll and cured with one of Fusions Aetek
UltraPak 400W/inch lamps.
Adhesion was tested after ink cure using 3M 610 Scotch Tape on an unscored print
surface. Prints from bench testing were rated for ink adhesion using a relative scale of 1 5, with
1 = poor and 5 = excellent. Prints from press trials were evaluated for adhesion by visually
assessing the quantity of ink left on the substrate after tape removal. A percent value was
assigned to the amount of ink remaining, with no ink removal = 100% adhesion and complete
ink removal = 0% adhesion.
RESULTS
Defining the monomers (s) to be used for the study
During pre-study work with monomers, a fatty acid modified polyester acrylate was used
as the base resin in a blend with the monomer being evaluated and photoinitiator. The monomer
evaluation showed positive adhesion results (Table 4) with TMPTA, HDODA, IBOA and
TRPGDA. IBOA was eliminated due to the high odor associated with this material and HDODA
was eliminated due to its tendency to attack and swell photopolymer printing plates.
Table 4- Evaluation of reactive diluents and monomers
Monomer

Reactivity

Adhesion

Flexibility

Isobornyl Acrylate

IBOA

Octyl/Decyl Acrylate

ODA

Tripropylene Glycol Diacrylate

TRPGDA

1,6-Hexanediol Diacrylate

HDODA

Trimethylopropane Triacrylate

TMPTA

Propoxylated Glycerol Triacrylate

GPTA

Trimethylolpropane Ethoxy Triacrylate

TMPEOTA

Reactivity, adhesion and flexibility were assessed on a scale of 1-5, 1=poor and 5=excellent

From the results of table 4, the monomers chosen for further evaluation in the UV inks
for press trial were Trimethylolpropane triacrylate (TMPTA) and Tripropylene glycol diacrylate
4

(TRPGDA) in a 1:1 ratio to combine the reactivity of TMPTA and the flexibility offered by
TRPGDA.
Defining the oligomer (s) to be used for the study
As part of the study, oligomers and monomers were assessed for basic properties on
metalized OPP, PET and PLA film substrates. Samples of each of the three substrates were
treated with the three types of surface treatment previously mentioned. The selected oligomers
were diluted with Trimethylopropane Triacrylate (TMPTA) to a viscosity of 500 mPa.s @ 25C.
After dilution, 10% Additol DX liquid photoinitiator blend was added to each sample. The
oligomer/monomer/PI blends were then printed on the substrate samples and each print was
assessed for tape adhesion and the results are listed in Table 5 below.
Table 5 Bench evaluation to define oligomers for the press trials: adhesion results

PET

Metalized OPP

PLA

Corona

Plasma

Flame

Corona

Plasma

Flame

Corona

Plasma

Flame

Amine modified polyester acrylate

Fatty Acid modified epoxy acrylate

Acrylate Aliphatic Urethane Acrylate

Epoxidized Oil Acrylate

Polyester Acrylate Bioligomer

Fatty Acid Modified Polyester Acrylate

Amine Modified Epoxy Acrylate

Aromatic Urethane Acrylate

Bisphenol-A Epoxy Acrylate

21

22

27

21

19

23

25

19

27

TOTAL

Adhesion was assessed on a scale of 1-5, 1=poor and 5=excellent

As shown in table 5, differences were identified in adhesion with generally increased

adhesion to the corona- or flame-treated films compared to the plasma-treated films. Also, it was
noted during the study that surface energy, and ultimately ink adhesion, of the flame-treated
substrates deteriorated within 2-3 days. The plasma- and corona-treated films retained surface
energy for a significantly longer period (up to 10 days) but while ink adhesion was maintained
on the corona-treated film as surface energy deteriorated, ink adhesion was significantly reduced
on the plasma-treated substrates.
The differences in adhesion were further analyzed by 1) overall adhesion by film and
treatment types and 2) overall adhesion by oligomer type. The data used for this analysis are
outlined in Tables 6 and 7 below.
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Adhesion analysis by film and treatment types (table 6) indicates that certain surface
treatments may be better suited for different film polymers. As a result, optimizing the surface
treatment and film combination may be another option, if conditions allow, to obtain increased
ink adhesion in addition to ink modification.
Table 6 Overall adhesion by film and treatment types

Corona
Plasma
Flame

Overalladhesion
(all inktypescombined)

27
25
23
21
19
17
15
PET

MetalizedOPP

PLA

Table 7 Overall adhesion by film and oligomer types

PET
MetalizedOPP
14

PLA

Combinedadhesion

12
10
8
6
4
2
0
Aminemod
PEA

FattyAcid
Acrylate
Epoxidized
PEA
modEA
AliphaticUA OilAcrylate Bioligomer

FattyAcid
Amine
ModPEA ModifiedEA

Aromatic
UA

BisphenolA
EA

Analysis of adhesion based on film and oligomer types (table 7), indicates that the ink
composition, specifically oligomer selection, significantly affects adhesion. This review was
used, in part, to help select the final ink composition.
Based on the results discussed above, it was decided to perform further evaluation for this
study using the top performing oligomer groups; fatty acid modified polyester acrylate and
polyester acrylate bioligomer. The starting formulation selected for further study is defined in
table 8 below.
Table 8- Ink starting point formulation

Pigment
Oligomer
Monomer(s)
Photoinitiator

18%
35%
37%
10%

RESULTS WITH FINAL FORMULATIONS

The final two ink formulations identified by bench-evaluation were subsequently tested at
Cytec Industries on a two-unit Aquaflex LC-1002 printing press using corona-treated OPP and
PLA films as in bench-testing. Additional PET film was unavailable at the time of testing. The
other treatment types used with the OPP and PLA films were also evaluated at 150 fpm and at
350 fpm in the Fusion Aetek UV unit.
At relatively low line speeds (150 fpm), acceptable adhesion was obtained with both inks
on both films and with all treatment types. As the line speed increased, adhesion to the coronatreated films was maintained with the ink based on the fatty acid modified polyester acrylate but
was reduced with the polyester acrylate bioligomer.
The reduction in adhesion might be related to a difference in reactivity between the two
oligomers. Also, at higher line speed adhesion to the plasma-treated films appeared to be less
than adhesion to the other two types of surface treatments.
It must be noted that the final ink formulations tested did not contain modifying resins
and/or additives that are commonly used in ink formulating to increase adhesion or tape release.
The following is a summary of the adhesion results with the final ink compositions.
Adhesion results with final ink formulations

PolyesterAcrylate
Bioligomer
FattyAcidModified
Polyester

150fpm
350fpm
150fpm

Flame
80%
50%

OPP
Plasma
80%
50%

Corona
95%
65%

Flame
85%
25%

PLA
Plasma
75%
25%

Corona
95%
50%

90%
80%

90%
75%

95%
85%

90%
90%

90%
70%

95%
90%

350fpm
Adhesion was visually assessed.
The % reported is the approximate ink coverage remaining in the tape area after the tape is removed.

CONCLUSIONS
Specific formula modifications, with additives and modifying resins, will be necessary to
provide optimum adhesion on a case-by-case basis. However, the following are the general
trends, results and observations from this evaluation:
1. Oligomer and monomer selection must be completed to match the type of film and
film surface treatment used to prepare the substrate for printing.
2. Differences in ink adhesion can be easily identified when the ink is printed on the
same base film finished with different surface treatments. At higher line speed,
adhesion to the plasma-treated film is less than adhesion to the corona- and flametreated samples of the same film.
3. As the treated substrates age, ink adhesion to the flame-treated film deteriorates
rapidly within a few days while adhesion to the plasma- and corona-treated films
remain for a longer period.
4. Fatty Acid Modified Polyester Acrylate-based ink displayed better adhesion than the
Polyester Acrylate Bioligomer-based ink especially at increased press speed.
Therefore, if the green property is desired in both film (e.g. PLA) and ink,
optimization must be completed with the ink composition to find the best balance of
properties.
5. The levels and types of monomers commonly used to improve ink adhesion, e.g.
HDODA, must be evaluated and optimized in order to obtain the best ink adhesion
while avoiding damage to the flexographic printing plate.

REFERENCES
[1] Seecharan, A. et al, Energy Cure (EC) Flexographic Inks for PLA Films, RadTech UV&EB Conference Proceedings, 2008.